Ternary and quaternary wax-resin composites for use in cosmetic and pharmaceutical preparations

ABSTRACT

A wax-resin composite is made by melting thermoplastic hydrocarbon resin, optionally with an antioxidant. The melted thermoplastic hydrocarbon resin and waxes are blended at a temperature sufficient to melt the waxes. After blending and melting, the blended thermoplastic hydrocarbon resin and waxes are allowed to solidify. Solidification is followed by post-processing the wax-resin composite mixture to form slabs, pastilles, flakes or other forms. A method for producing a wax-resin composite comprises at least partially solvating a thermoplastic resin in a solvent to form a resin-solvent blend. This may be done at a heat of 80-85° C. A composition of molten wax is blended with the resin-solvent blend. The resin-solvent blend and a molten wax are blended to form a wax-resin blend. This is followed by removing the solvent from said wax-resin blend.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims priority as a divisional under 35 U.S.C. 121 toU.S. patent application Ser. No. 12/410,550 filed on Mar. 25, 2009,entitled “TERNARY AND QUATERNARY WAX-RESIN COMPOSITES FOR USE INCOSMETIC AND PHARMACEUTICAL PREPARATIONS,” which claims priority under35 U.S.C. 119(e) to U.S. Provisional Application Ser. No. 61/044,301,entitled “COSMETIC AND PHARMACEUTICAL COMPOSITIONS COMPRISING WAX-RESINCOMPOSITES,” filed Apr. 11, 2008, each of which are incorporated byreference in their entirety.

TECHNICAL FIELD

The present invention relates to a complex of a thermoplastichydrocarbon resin processed together with a blend of waxes. Inaccordance with certain embodiments of the present invention, thecomplexes may be used in cosmetic and pharmaceutical compositions. Thecomplex may be in the form of a ternary or quaternary composite.

Hydrocarbon-based resins have excellent adhesion that helps to improvewear. They are not used very frequently in cosmetics and pharmaceuticalbases, because the adhesion translates to poor sensory properties whenapplied to the skin, hair, lashes and nails. It also results in anocclusive film on the skin. Kobo Products Inc. currently manufacturessolutions of hydrogenated polycyclopentadiene for cosmetic use. Ourinvention focuses upon hydrocarbon resins derived from petroleum anddoes not include hydrocarbon resins produced from, for example plantderived, terpene or rosin.

SUMMARY OF THE INVENTION

The invention introduces new complexes that may be in the form ofcrystalline solids or which may be incorporated into suspensions whichhelp to both facilitate incorporation of the polymer into various phasesand also provide a wider range of materials for flexibility offormulation use in the end products. By ternary and quaternarycomposites is meant the combination of resin (e.g. Escorezpolycyclopentadiene) with two or three waxes.

Though adhesion is required and is a component of long-wear products,lesser amounts of adhesion can still achieve excellent results,especially when combined and balanced with materials that are abhesiveor have non-stick properties, especially waxes. The ternary andquaternary complexes are formed from the resin and wax blends. Anadditional component, an antioxidant, is typically included to insurestability of the matrix for odor and chemical integrity. Hydrocarbonwaxes or natural waxes containing hydrocarbons have been found to modifyand improve the properties of a tackifier polymer, hydrogenatedpolycyclopentadiene. This complex forms a hydrocarbon wax-resincomposite. This material described herein can be used for cosmetic andpharmaceutical formulations to improve rub-resistance, adhesion andflexibility of the final film on the skin, hair, lashes and nails,thereby improving overall performance. Surprisingly, applicants foundthat even very small amounts of solid waxes significantly modified theproperties of hydrogenated polycyclopentadiene. The inclusion andcomplexation of the wax with the polymer provided a balance between theadhesion and sensory acceptability properties mentioned above.

BRIEF DESCRIPTION OF THE DRAWINGS

The invention may be understood with reference to the drawings in whichFIG. 1 is a graphical representation of rub-resistance transfer for arange of materials; and FIG. 2 is a graphical representation of adhesiontransfer for a range of materials.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

In accordance with one aspect of the present invention, the hydrocarbonresin is first partially solvated with a hydrocarbon solvent to blendthe waxes and hydrocarbon resin together in a homogenous mixture. Thisproduced clear solutions when mixed with molten wax. Blending the moltenwax with the resin alone did not result in a complete solution for mostblends at normal processing temperatures for the waxes. For the solventprocess, the composite was heated below the softening point of the resinwhich is above 100° C. Plasticizing the resin with a solvent andhydrocarbon waxes, makes it possible to process the composite withinnormal ranges of the melting points of the waxes. Through controlledevaporation of the solvent, solid granules via crystallization andsemi-solid dispersions are produced.

Another aspect of the invention includes a thermal process, whereby thetemperatures can exceed 100° C. An antioxidant was included to preventany changes in the waxes. The thermal process allows for both theformation of the composite, as well as direct post-processing of thecomplex into pastilles and other shapes.

Controlled temperatures result in semi-transparent to transparentsolids, in the form of pastilles and other shapes. Equipment other thanthose listed in the basic lab process and described in this document mayalso be used to produce these complexes. A Processall or rotaryevaporators, etc. may also be used.

According to specific embodiments, the composition may comprise at leasttwo to three different waxes in combination with the hydrogenatedpolycyclopentadiene. One wax may be a hydrocarbon wax such as apolyethylene wax, a synthetic wax or a petroleum type wax. They may belinear or branched. The second wax may be a natural wax which containshydrocarbons or has a hydrocarbon-like structure or component to it,such as carnauba wax. Natural waxes improve the affinity of theinventive end product to a variety of carriers. The third may beselected from any of the classes of waxes: hydrocarbon, synthetic,petroleum or natural.

The complex can be used for cosmetic and pharmaceutical compositions,such as emulsions (oil-in water, water-in-oil, as well as silicone,hydrocarbon and ester emulsions, both volatile and non-volatile), hotpour, anhydrous, powders, sunscreens, delivery patches, ointments,encapsulation, surface-treatments, binders and general coatings toimprove wear. The complex may be used in either the internal or externalphase or both phases simultaneously. The invention can also improve thestability of films on the skin, hair, nails and lashes for cosmetic andpharmaceutical compositions for products such as lipstick, mascara, nailpolish, eye shadow, sunscreens, etc.

These wax-resin complexes may be added to emulsions both prior toemulsification and also post emulsification. They may be added to otherproduct forms such as anhydrous systems and powders during the initialstages of processing or upon letdown and during cooling or during thefinishing stages of the product.

Composites create a synergism producing material properties unavailablefrom the individual constituent materials. By solubilizing the adhesivehydrocarbon resin together with blends of waxes and an antioxidant, anumber of benefits may be realized in accordance with certain aspects ofthe present invention.

First, the complex facilitates the incorporation of the high meltinghydrocarbon resins (softening point 85° C. to 125° C.) into cosmetic andpharmaceutical vehicles. Hydrocarbon resins can take significantly longperiods of time to completely solubilize even when using high shear andhigh temperature. By capturing the resin within a compatible wax matrix,the time to solubilize the resin may be reduced to minutes using onlylow shear. When heated, the wax crystals melt within the resin matrixand disrupt the polymer structure enough to allow solubilization withina solvent. This results in a solubilized complex that can be used morereadily in production for cosmetics and pharmaceuticals than the polymeritself and with better performance.

In addition to this, abhesive (or non-stick) properties of binary andternary wax blends can balance the strong adhesion of the hydrocarbonresin, resulting in a material matrix that optimizes adhesion forapplication to the skin, hair, lashes, lips and nails.

Third, the use of binary and ternary blends of waxes can reinforce thehydrocarbon resin thereby improving rub-resistance. The resulting filmmay be tougher and more resistant to abrasion. Water-resistance may beincreased when the complex is incorporated into formulations due to thehydrophobic nature of the components.

A fourth benefit is that flexibility and breathability of thehydrocarbon resin may be improved by the addition of binary and ternarywax blends which alter the structure of the resin. The addition of waxesto the resin increases both ductility and breathability of the formedfilm.

Finally, overall physical stability of cosmetic and pharmaceuticalproducts may be improved for both anhydrous suspensions and emulsions,as the matrix of the waxes and hydrocarbon resin combine to envelope thesolvents or external phases of the systems. It can also improvestability when used in the internal phase of an emulsion.

Composites are engineered materials and are generally made of two ormore components. Composite materials, in accordance with the inventionare created by combining a matrix with another material forreinforcement. The matrix material surrounds and supports thereinforcement materials binding them. The reinforcements impart theirspecial mechanical and physical properties to enhance the matrixproperties. For example, one may incorporate fibers. The fiber can be asilica, graphite, or a polymer. A polymer that may be used for thispurpose is polyethylene or polyethylene-like materials.

However, even when the polyethylene is not elongated like a fiber and ismore plate-like or crystalline, we have found that reinforcement stilloccurs in our invention, though of a somewhat different nature with moreflexibility. Compatibility is key to reinforcing the matrix and sohydrocarbon waxes or hydrocarbon-containing waxes provide goodfunctionality with hydrocarbon resins. The compatibility of the mixturescan be determined using cloud point measurements. The lower the cloudpoint temperature, the better the compatibility.

For composites, the matrix may be a thermoset or thermoplastic material.An example of a thermoset is an epoxy resin. However, polymers can alsobe used for this purpose. An example of thermoplastic polymers is apolyimide.

For certain aspects of the present invention a thermoplastic polymer,hydrogenated polycyclopentadiene, functions as the matrix.

The waxes for use in the present invention should crystallize or freezeprior to or together with the setting of the resin. The waxes should becompatible with the resin. If the melting point of the wax is too low,the resin will crystallize first and then be surrounded by the wax whichmelts at a lower temperature. The waxes should be optimized with thehydrocarbon resin for co-crystallization and reinforcement of thematrix. This results in the production of transparent solids, such assemi-transparent, crystalline pastilles. These pastilles or other formsmay also incorporate colors, pigments or dyes which have beenpre-dispersed or solubilized as part of the overall complex.

Chain molecules of many natural and artificial polymers are arranged ina way which is at least partially crystalline. Polyethylene chains arearranged in a zigzag pattern which results in a large reduction of thestiffness of the polymer. Before the plastic can break, many of thecrystals have to unfold making it very tough. One example of theinvention is the use of polyethylene wax in combination with another waxto form the composite with the matrix, hydrogenated polycyclopentadiene.The addition of the polyethylene to the complex helps to improve theoverall resistance of the film to abrasion.

The composition contains, for example, a solid, crystalline orsemi-crystalline phase of: polyethylene or a petroleum wax or asynthetic wax, a hydrocarbon resin, and a natural wax such as carnaubaor candelilla wax, also containing significant amounts of hydrocarbons.In this preferred composition, the wax co-crystallizes or eithercrystallizes just slightly before the T_(g) (glass transitiontemperature) of the resin, thus forming a crystalline orsemi-crystalline phase dispersed throughout a continuous matrix(hydrocarbon resin). The inventive compositions may employ fourcomponents.

As a first component, hydrocarbon thermoplastic resins may be used. Theorganic resins utilized herein can be one or more of a broad group ofmaterials which are compatible at elevated temperatures at the desiredratio with the waxes. By “elevated temperatures” is meant thetemperature of manufacture which normally is at least above the meltingpoint of the highest-melting component of the waxes. The melting points(softening point) or melting ranges of the preferred thermoplasticresins is normally in the range of about 50° to about 150° C.,preferably between about 85 to about 115° C. In accordance with certainembodiments, the resins are selected to have a melting point close tothe melting point of the polyethylene, synthetic wax or hydrocarbon waxor other waxes in the complex. The preferred resins belong to a class ofmaterials referred to in industry by the term “hydrocarbon resins”.Hydrocarbon resins are defined by the Kirk-Othmer Encyclopedia ofChemical Technology, Second Edition, Volume 11, John Wiley & Sons, NewYork, N.Y., 1966, page 242 et seq., as the readily thermoplasticpolymers of low molecular weight derived from coal-tar fractions, fromdeeply cracked petroleum distillates, and from turpentine. Thesehydrocarbon resins (which are not hydrocarbon in the strictest sense ofthe term, since they may contain minor amounts of oxygen or otherelements occurring in these natural materials) generally have amolecular weight of about 300 to about 1,200, preferably about 300 toabout 900. Preferred resins are primarily derived from dicyclopentadienestreams (DCPD). Aromatic streams can also be used to modify DCPD. Bothstreams are byproducts of the commodity olefins ethylene and propylene.

Typical hydrocarbon resins useful in the practice of the inventioninclude hydrogenated hydrocarbon resins. From the standpoint ofobtaining high compatibility with polyethylene wax and the other waxes,the “Escorez” resins (Exxon Mobil Chemical Company) have been found tobe particularly suitable. These hydrocarbon resins are hydrogenatedpolycyclopentadienes that meet requirements for food packaging includinglow color and low odor. Escorez 5400 and 5415 are examples of thisresin. They are generally used in hot melt adhesives for coating foodpackaging and other varied uses, but they are also of value forcosmetics and pharmaceuticals. The present invention addresses many ofthe issues associated with their potential use for cosmetic andpharmaceutical applications.

The polymers of cyclopentadiene are readily produced in known manner bythe polymerization of cyclopentadiene or polymers thereof, for example,by heating over an extended period at temperatures of about 150° C. to250° C. or by the action of catalysts. In this manner, mixtures ofunsaturated hydrocarbons are obtained, the carbon skeletons of whichconsist of a series of five-membered rings, a double bond being presentin each end ring of the polymer molecules. It is of advantage for somepurposes to saturate these double bonds by hydrogenation, whichhydrogenation may be effected in a simple manner, for example, by atreatment with hydrogen under pressure in the presence of active nickel.Among the saturated hydrocarbons of this kind those containing two ormore condensed five-membered rings are preferred for use in theresin-wax complexes.

The higher saturated polymers of cyclopentadiene, particularly thehydrogenated pentamer, are extremely useful compounds for incorporationin the resin-wax compositions. They are solids at 20° C. When mixed withwaxes of natural or synthetic origin containing hydrocarbons, either adecrease or an increase in the melting point of the natural or syntheticwaxes occurs depending on the polymers used and the quantitativeproportions of the constituents in the mixture. Wax-resin compositionsin accordance with the invention, in which the cyclopentadienederivative is a hydrocarbon, may be produced which, in addition to theaforementioned properties, may have melting points that extend above100° C. but may also be less than 100° C.

As a second component hydrocarbon waxes, polyethylene waxes, syntheticwaxes or petroleum waxes may be used. The crystalline polyethylenesfound useful in this invention are those which have a specific gravityof about 0.90 to about 0.98, preferably about 0.91 to about 0.95, asdetermined by the density gradient technique (ASTM Test D 1505-63E).These polyethylenes have been found to have molecular weights of about500 to about 10,000, preferably about 1,000 to about 3,500, and exhibitan average viscosity of less than 500 cps at 140° C. (Brookfieldviscometer, Model LVT). The preferred polyethylenes are highlycrystalline. The term “crystalline”, as used herein, characterizes thosepolyethylene polymers which have a definite visible crystal structure asobserved through a petrographic microscope. Polyethylenes are alsocommonly referred to or described as waxes due to their wax-likeproperties.

The following is a non-limiting list of typical commercially availablepolyethylene polymers useful in the invention. All of these polymers aremanufactured by Honeywell Personal Care and have “Asensa” commercialgrade numbers or are manufactured by New Phase Technologies asPerformalene or Performa V series. Polymer grades Asensa SC 220, SC 210,SC 201 810A, 820A, 1702 and SC 221 are some examples of non-emulsifiablepolyethylenes. They were formerly known as ‘AC’ grades manufactured byAllied Chemical.

Melt. pt. Density Polymer Grade (° C.) (g/cc) at 25° C. Asensa SC 201106 0.92 Asensa SC 210 101 0.91 Asensa SC 220 115 0.93 Asensa SC 221 1150.93 Asensa SC 222 115 0.93 Performa V 103 74 0.92 Performa V 253 670.92 Performa V 260 54 0.90 Performalene 400

Synthetic waxes such as amide waxes, ester waxes, etc., or any wax-likematerial which can be upgraded in accordance with this invention. Theonly requirements are that the hydrocarbon polymer, hydrogenatedpolycyclopentadiene, be compatible with the wax or wax-like material.Synthetic waxes include those disclosed in Warth, Chemistry andTechnology of Waxes, Part 2, 1956, Reinhold Publishing, the contents ofwhich are hereby incorporated by reference. The waxes most useful hereinhave melting points from about 55° C. to about 115° C. and are selectedfrom the C8 to C50 hydrocarbon waxes. Synthetic waxes includelong-chained polymers of ethylene with OH or another stop lengthgrouping at the end of the chain. Such waxes include the Fischer-Tropschwaxes as disclosed in the text disclosed above at pages 465-469 andinclude Rosswax, available from Ross Company and PT-0602 available fromAstor Wax Company or New Phase Technologies synthetic waxes. Siliconewaxes may also be used. The setting time of the wax-resin composite maybe reduced by increasing the concentration of a synthetic wax. The term“hydrocarbon wax” is a wax composed solely of carbon and of hydrogen.Hydrocarbon wax and oil emollients include branched and unbranchedhydrocarbons such as petrolatum, microcrystalline waxes, paraffins,ceresin, ozokerite, polyethylene and the like.

As a third component, natural waxes containing hydrocarbons orhydrocarbon like structures may be used. Naturally occurring waxes orthose naturally occurring and processed or chemically modified may bemade into the composite for this invention. These include petroleumwaxes such as paraffin wax, microcrystalline wax, etc., naturallyoccurring waxes such as beeswax, carnauba, candelilla, jojoba, montan,peat wax, ouricury wax, soy wax, esparto wax, rice wax, sugar cane wax,maize wax, bayberry, etc. or any wax-like material which can be upgradedin accord with this invention, such as hydrogenated castor oil. Theprimary requirement is that the hydrocarbon polymer, hydrogenatedpolycyclopentadiene, be compatible with the wax.

The waxes suitable for use in the present compositions include, but arenot limited to, those selected from the group consisting of candelilla,beeswax, beeswax having free fatty acids removed (modified beeswax),carnauba, candelilla, ozokerite, ceresin, paraffin, microcrystallinewaxes, and mixtures thereof. More particularly the waxes may be selectedfrom the group consisting of microcrystalline, candelilla, modifiedbeeswax, carnauba, ozokerite, paraffin, ceresin and mixtures thereof.Waxes such as triglycerides or glycol diesters of C₁₈ to C₃₆ fatty acidsare also suitable.

As a fourth component natural waxes containing hydrocarbons orhydrocarbon-like structure and hydrocarbon waxes, such as polyethylenewaxes, synthetic waxes or petroleum waxes may be used. See thediscussion of the second and third components. The fourth component isinclusive of all of the above in its description referring to the secondand third components.

It is within the scope of this invention to add low boiling solventsand/or plasticizers and antioxidants, as previously described. Theplasticizer or flexibilizer materials lower the melt viscosity andincrease flexibility. Among the suitable plasticizers are: mineral oil,soya oil, isostearyl isonananoate, and safflower oil and other oils andesters. Anti-oxidants that are preferred are tocopherols, but are notlimited to these alone. The composition may contain antioxidantcompounds with sterically hindered phenolic hydroxyls. An antioxidantconcentrated in 7,8-dimethyltocol can be used.

Test Results for Rub Resistance

Films were created from a series of water-in-silicone/isododecaneformulations containing pigments and a wax-resin composition inaccordance with certain aspects of the present invention at variousratios or blends of the waxes and resin components. These films wereabraded at a constant pressure and weight and then transferred to imageanalysis software for results. Results are shown in FIG. 1 Rubresistance demonstrates the strength and flexibility of the filmsincorporating the wax/resin complexes.

Test Results for Adhesion

Films were created from a series of water-in-silicone/isododecaneformulations containing pigments and a wax-resin composition inaccordance with certain aspects of the present invention at variousratios or blends of the waxes and resin components. These films werepressed on adhesive tape at a constant pressure and weight, removed andthen transferred to image analysis for results. This testingdemonstrates the varying degrees for strength of adhesion of the filmsincorporating the wax: resin complexes and leads to optimization of theinvention. Results are shown in FIG. 2.

Test Results for Gloss

Films were created from a series of water-in-silicone/isododecaneformulations containing pigments and a wax-resin composition inaccordance with certain aspects of the present invention at variousratios or blends of the waxes and resin components. These films werethen measured with a gloss meter. This testing demonstrates the synergyof combining specific waxes in combination with the resin to improvegloss of finished products. Results are in Table 1. Increasing glossnumber indicates higher gloss.

Results were as follows:

TABLE 1 Water-in-Silicone Formulations Gloss Results for Wax-incorporating wax-resin complex Resin Complex No resin 1.05 Resin at a100% level 1.06 Binary Waxes:Resin Ratio (1:4) 1.52 (Optimized) BinaryWaxes:Resin Ratio (1:1) 1.32 Binary Waxes:Resin Ratio (4:1) 1.37

In accordance with the invention, a hydrocarbon resin, hydrogenatedpolycyclopentadiene, can be blended (either individually, or in binaryand ternary blends) of waxes that are 1) hydrocarbon-based (such asparaffin, ozokerite, microcrystalline and synthetic waxes, polyethylene,etc.), 2) hydrocarbon waxes modified with silicone (such as alkylsilicone waxes) or fluoro moieties, 3) silicone or fluoro waxes, 4)natural waxes that contain high levels of hydrocarbons (such ascandelilla, beeswax, carnauba, etc.), 5) hydrogenated natural waxes ormodified versions thereof, 6) synthetic waxes such as Fischer-Tropschwaxes or amide waxes, ester waxes, etc., or 7) the composite materialsdescribed herein may be prepared by various processes including, withoutlimitation, by 1) recrystallization from a molten mixture of solid waxesor polymeric waxes and a solid hydrocarbon resin, 2) recrystallizationfrom a molten mixture of solid waxes or polymeric waxes and a partiallysolvated hydrocarbon resin, or 3) recrystallization from a moltenmixture of solubilized waxes or polymeric waxes and a fully solubilizedhydrocarbon resin.

In accordance with the invention, solid composite wax-resin that ispowdered, flaked, prilled, molded or extruded is produced.

Waxes (individually or in combinations) may be incorporated in a rangeof about 2 to about 98% by weight. The hydrocarbon resin may range fromabout 2% to about 98% by weight

In accordance with the invention, 1 to 99% hydrogenatedpolycyclopentadiene may be dissolved in 1 to 99% wax which is processedat or above the temperatures of the softening point of the resin.

In a solvent based process, 10 to 90% hydrogenated polycyclopentadieneis dissolved in volatile hydrocarbon (1 to 50 parts) which is added tomolten wax at a level of 10 to 90% and processed at or below thesoftening point of the resin.

-   -   The solvent process of the invention yields solid/resin wax        composites that are easier to process, melting at around 50°        C.-60° C., as compared to resin which softens around 100° C.

Even very small amounts of solid waxes significantly modified theproperties of hydrogenated polycyclopentadiene with regards toflexibility and other properties and vice-versa. Depending upon theratio of waxes, in accordance with certain embodiments, the waxes wereable to modify the polycyclopentadiene to improve its structure anddecrease its tack. Thick films of hydrogenated polycyclopentadieneremain tacky indefinitely while thin films of the material are brittle,in accordance with certain embodiments. The addition of waxes to thesubstance improved both thick and thin films. Similarly the hydrogenatedpolycyclopentadiene could be modified with the waxes to form new,malleable structures that could be drawn out like filaments.

Very small levels of waxes in ratio to the polymer formed a compositematerial having similar properties to standard accepted cosmeticmaterials such as polybutene and polyisobutene, etc. Higher levels ofwaxes in ratio to the polymer resulted in new materials with uniqueproperties for cosmetics and pharmaceuticals.

Wax-Resin Composite Formulas_Produced Via a Solvent and Thermal Process

Throughout this specification, the amount of ingredients by weight arereferenced to the weight of the total composition, unless otherwisespecified. The following examples illustrate the invention.

Thermal Process

CRYSTALLINE SOLID FORM-THERMAL PROCESS INGREDIENTS EXAMPLE 1. [Total 100parts] (Resin/Antioxidant Phase Koboguard 5400 79.70 Covi-Ox T70 0.3080.00 (Wax Phase) Asensa SC210 13.34 Carnauba Wax 6.66 20.00 EXAMPLE 2.[Total 100 parts] (Resin/Antioxidant Phase) Escorez 5415 49.70 Covi-OxT50 0.30 50.00 (Wax Phase) Microcrystalline Wax 33.34 Candelilla Wax16.66 50.00 EXAMPLE 3. [Total 100 parts] (Resin/Antioxidant Phase)Escorez 5415 79.67 Rosemary Oleoresin 0.33 80.00 (Wax Phase) Asensa SC810A 13.34 Ceresin Wax 6.66 20.00 EXAMPLE 4. [Total 100 parts](Resin/Antioxidant Phase) Escorez 5400 59.66 Rosemary Oleoresin 0.3360.00 (Wax Phase) Performa V103 26.66 Ceresin Wax 13.34 40.00Thermal Process Procedure

The following procedure is used in examples 1-4

-   -   1. Tare (weigh) a 1200 ml stainless steel beaker. Put the resin        and antioxidant into the beaker. under a fume hood.        Alternatively, an explosion-proof mixer under the fume hood may        be used. Fill a bain marie (water bath—2000 ml SS beaker) with        50/50 propylene glycol/tap water mixture or a bath of mineral        oil.    -   2. Immerse the 1200 ml SS beaker into the bath. The bath should        be heated to 105° C. to 110° C. Do not allow the batch to exceed        a temperature of 120° C. Temperature may be monitored directly        using a thermometer immersed in the melted resin. Monitor the        batch at all times during preparation.    -   3. Be sure the 1200 ml stainless steel beaker is completely        immersed in the bath up to the level of the resin.    -   4. After the resin is melted (approximately 105° C.), add the        waxes, which are at room temperature, to the beaker. Heat to        achieve a temperature close to but not above 120° C. Take care        to ensure that the level of materials in the beaker is not above        the level of the bath.    -   5. Cover the beaker with aluminum foil during the heating        process.    -   6. Allow the blend to melt almost completely which occurs at a        temperature in the range of 110-120° C. Once this temperature        has been achieved, and almost complete melting observed, start        to mix with a stirrer. The softening/melting process may take        60-90 minutes to complete. The softened resin will solubilize in        the other materials as stirring is begun.    -   7. When the solution appears clear begin stirring slowly with a        Caframo or Lightnin' mixer until the polymer is solubilized.        Solubilization of the polymer may be determined by observing the        clarity of the solution and which should be transparent as        opposed to cloudy.    -   8. After the solution has been stirred to melt all solids and is        homogenous continue slow stirring for an additional 15 minutes.        The object of this additional staring is to remove air from the        product.    -   9. Record weight of the beaker and product.    -   10. Pour the batch into silicone or teflon enamel coated molds        or pans. Cover with aluminum foil.    -   11. Allow the melt to solidify at room temperature. Record        weight or batch yield.        Solvent Process

As an alternative to the thermal process described above, in accordancewith the invention, the crystalline solid composite wax-resin matricesmay be made by a solvent process.

Crystalline Solid Form

Produced by the Solvent Process

EXAMPLE 5. [Total 120 parts] (Solvent/Antioxidant Phase) Shell Sol OMS19.67 Covi-Ox T70 0.33 20.00 (Wax-Resin Phase) Escorez 5400 80.00 AsensaSC210 13.34 Carnauba Wax 6.66 100.00 EXAMPLE 6. [Total 120 parts](Solvent/Antioxidant Phase) Isopar C 19.67 Covi-Ox T50 0.33 20.00(Wax-Resin Phase) Escorez 5380 50.00 Microcrystalline Wax 33.34Candelilla Wax 16.66 100.00 EXAMPLE 7. [Total 120 parts](Solvent/Antioxidant Phase) Isododecane 19.67 Rosemary Oleoresin 0.3320.00 (Wax-Resin Phase) Escorez 5415 80.00 Performa V103 13.34 CeresinWax 6.66 100.00 EXAMPLE 8. [Total 120 parts] (Solvent/Resin/AntioxidantPhase) K5400IDD (Kobo) 77.67 Rosemary Oleoresin 0.33 78.00 (Wax Phase)Performa V103 28.00 Ceresin Wax 14.00 42.00Solvent ProcessLaboratory Procedure

Examples 5-8 are made using the following process

-   -   1. Tare (weigh) a 1200 ml stainless steel beaker. Put        antioxidant and solvent into beaker under a fume hood. Use an        explosion-proof mixer under the fume hood. Fill a bain marie        (water bath—2000 ml stainless steel beaker) with tap water.        Slowly begin heating.    -   2. Immerse the 1200 ml stainless steel beaker into the bath. Do        not allow the batch to exceed a temperature of 100° C. at any        time. Monitor the batch at all times during preparation for        safety reasons, as temperature exceeds the flashpoint of the        solvent.    -   3. Be sure the 1200 ml stainless steel beaker is completely        immersed in the steam bath up to the level of where the liquid        and waxes are present.    -   4. Do not cover the beaker with aluminum foil. Weigh and add,        waxes and the resin which are at room temperature, at about        30-35° C., and begin heating to 90-95° C. in the water bath.        Record weight of the beaker and product to monitor the extent to        which the solvent has been boiled off.    -   5. When the solution appears clear begin stirring slowly with a        dispersator.    -   6. Increase the dispersator speed and continue stirring until        all of the solvent has evaporated which is determined via weight        measurements.    -   7. Pour the batch into silicone or teflon enamel coated molds or        pans. Cover with aluminum foil.    -   8. Allow the melt to solidify at room temperature. Record weight        or batch yield.

Cosmetic Product Application Examples

The wax-resin composite materials manufactured in accordance withexamples 1-8 above, may be used to make a wide variety of cosmeticproducts.

In making the various cosmetic products illustrated by the followingexamples, any of the composites whose fabrication is explained inconnection with the above Examples 1-8, may be used, although differentcharacteristics in feel, fluidity, etc. may be noted. Particular ones ofthe Examples 1-8 with particular waxes and/or other ingredients may besuggested below. Moreover, combinations of the Example 1-8 products in awide range of proportions is expected to yield products with excellentcharacteristics. In this application, the convention of listingingredients and the process of mixing the same is followed. CFTAnomenclature (e.g. (and)) is also sometimes used herein.

Example 9 Cosmetic O/W Mascara Incorporating the Wax-resin CompositeExample of a Wax (Oil)-in-water Emulsion Product

Ingredients Phase I Deionized Water 47.65 Natrosol 250HR 0.80 (gumstabilizer) Methylparaben 0.20 (preservative) Butylene Glycol 3.00(humectant/ plasticizer) Phase II Ammonium Hydroxide (30% 0.35(neutralizing agent) Solution) Phase III Hydrogenated Polycyclo- 3.00(or any products of pentadiene (and) Polyethyl- Ex. 1-8) ene (and)Ozokerite (and) Tocopherol Stearic Acid 2.00 (emulsifier) SyntheticBayberry Wax 1.50 (emollient wax) White Beeswax 3.00 (thickener) LanolinUSP 1.00 (emulsifier) C18-36 Triglycerides 3.50 (stabilizer/thickener)Phase IV Black NF (black iron oxide) 8.00 (colorant) Silica - MSS500W(Kobo) 3.00 (textural agent) Phase V Daitosol 5000AD Emulsion 22.00(film-former) Latex (Daito) Phase VI Germaben II/ISP (a preserva- 1.00(preservative) tive) (ISP) 100.00Process:

-   -   1. Prepare this entire batch under a fume hood and with        appropriate respirator and cartridges for working with ammonia.        Except where specified otherwise, materials are at room        temperature. Add the aqueous Phase I to a 2000 ml stainless        steel beaker and begin mixing with propeller agitation. After        mixing for 10 minutes, begin heating to 90 C in a water bath        covering the beaker with aluminum foil.    -   2. Keep ammonium hydroxide refrigerated and at a temperature of        approximately 5-10° C. The ‘refrigerated’ aqueous ammonia Phase        II should not be added until just prior to emulsification in        Step 3 to avoid the ammonia volatilizing off.    -   3. In a separate beaker, combine Phase III (one of the wax-resin        composites of Examples 1-8 and other waxes) at room temperature        and then heat to 90 C.    -   4. When both phases (I and III) are at temperature (90 C), add        Phase II ammonia very slowly to Phase I, keeping the beaker        covered as much as possible with aluminum foil.    -   5. Then add Phase III to the aqueous mixture of Phase I and        Phase II. Continue mixing with propeller agitation and maintain        temperature at 90° C. for 15 minutes keeping the beaker covered.        Propeller agitation may be done with a Lightnin mixer.    -   6. Phase IV powders should be pulverized to a size of, for        example, about 30-2000 nm, or in the case of other pigments as        large as about 5000 nm. Sift the powders into the heated batch        while continuing to mix with propeller agitation. Once powders        are completely added, switch from propeller mixing to        homogenization. Homogenization may be done with a conventional        homogenizer such as a Silverson. Homogenize until pigment is        completely dispersed. Once pigment is fully dispersed, change        back to propeller agitation. Begin air cooling with continued        propeller agitation. Air cooling may be done by removing the        beaker from the bath.    -   7. Add the emulsion latex (Phase V) to the batch after the        temperature drops to about 60-65 C.    -   8. Allow the batch to cool to about 55° C. and weigh, noting        weight loss as compared to starting materials and add Q.S. to        compensate for the water loss measured at 55 C.    -   9. When batch has cooled to 50 C, add the preservatives        (Phase VI) and continue stirring.    -   10. Cool to 25-30 C. Put product into mascara bottles and seal.

Example 10 Pharmaceutical Sunscreen Using the Wax-Resin CompositeExample of Water-in-oil Emulsion Product

Ingredients: % Wt. PHASE 1 Optinally, for example, 7.00 (or products ofPolyethylene (and) Car- examples 1-8 nauba Wax (and) Hydroge- natedPolycyclopentadiene (and) Tocopherols or combinations) Permethyl 99A7.79 (solvent) PHASE 2 Lucentite SAN-P 2.00 (thickener/stabilizer)Phenoxyethanol 0.66 (preservative) PHASE 3 PM9P50M170 Titanium 30.00(inorganic sunscreen Dioxide (and) Isododecane agent pigment (and)Alumina (and) Titanium Dioxide Methicone (and) Poly- dispersion)hydroxystearic Acid Tospearl 2000B 3.38 (spherical powder to improveapplication) Cyclomethicone and PEG/ 6.80 (surfactant/primary PPG-20/15Dimethicone emulsifier) PHASE 4 Sorbitan Oleate 0.75 (secondaryemulsifier) Sorbitan Isostearate 0.75 (secondary emulsifier)Propylparaben 0.10 (preservative) PHASE 5 Sodium Chloride 1.00 (emulsionstabilizer) Deionized Water 17.70 (solvent) Methylparaben 0.10(preservative) PHASE 6 Glyceryl Tribeheante 1.65 (thickener) SyntheticBeeswax 1.10 (thickener) dl-alpha Tocopherol 0.10 (antioxidant) PHASE 7Velvesil 125 (GE) 17.70 (texture modifier) PHASE 8 Vanillin FCC 0.02(fragrance) Phenoxyethanol USP 0.10 (preservative) PHASE 9 Deionizedwater 1.00 (solvent/carrier) dl-Panthenol 0.30 (vitamin) *TOTALS: 100.00

Example 12 Personal Care Antiperspirant Incorporating InventiveWax-Resin Composite Ternary Example of an Anhydrous Product

Ingredients: % Wt. Permethyl 99A (isododecane) (solvent) 41.00Hydrogenated Polycyclopentadiene and Synthetic Wax and 5.00 Carnauba andTocopherols (or product of examples 1-8) Summit AZG-370 (Summit)(aluminum zirconium 25.00 tetrachlorohydrex glycine) (activeantiperspirant agent) Lanette Wax 18 (Henkel) (stearyl alcohol)(structural agent) 16.00 Castorwax MP80 (CasChem) (hydrogenated castoroil) 5.00 (structural agent) Dow Corning 9040 (cyclomethicone (and)dimethicone 8.00 Crosspolymer) (polymeric textural agent) 100.00Procedure:

-   -   1. Add all ingredients (wax-resin composite, solvent, waxes,        etc.) to a 600 ml stainless steel beaker. Cover the beaker with        aluminum foil.    -   2. Mix at ambient temperature with a propeller mixer in a water        bath until all materials are dispersed evenly.    -   3. Begin heating to 70-80° C. by heating of the water bath while        mixing. After all waxes have melted to produce a uniform        solution, remove the batch from the heat source, for example by        removing it from the water bath. Continue to mix.    -   4. When the temperature of the solution reaches 60° C., pour        into antiperspirant containers. Allow to cool to ambient        temperature.

Example 13 Cosmetic O/W Eyeliner Incorporating the Wax-Resin CompositeQuaternary Example of Wax Oil-in-water Emulsion

Formula: % Wt. Phase A Deionized water 61.05 (solvent) Phase B Xanthangum 0.50 (stabilizer) Carboxymethyl cellulose 0.40 (stabilizer)Magnesium aluminum silicate 0.40 (suspending agent) Phase C Deionizedwater 12.00 (solvent) PVP K30 8.00 (film-former) Phase D Iron oxides(black) 6.50 (colorant) Phase E Lecithin 0.20 (wetting agent)Triethanolamine, 99% 1.00 (emulsifier) Methylparaben 0.35 (preservative)Phase F Stearic acid 2.50 (emulsifier) Hydrogenated Polycyclopentadieneand 5.00 (or any products of Polyethylene and Beeswax and Paraffin Ex.1-8) Wax and Tocopherols Sorbitan sesquioleate 1.00 (emulsifier) Phase GDeionized water 1.00 (solvent) Imidazolidinyl urea 0.10 (preservative)100.00Procedure:

-   -   1. Put the phase A water into a stainless steel beaker. Heat the        water (Phase A) to 85° C. using a water bath.    -   2. Dry blend the phase B ingredients (which are polymer gums)        and add to A using a propeller mixer at medium/high speed. Mix        until the gums are completely hydrated., approximately 15-20        minutes.    -   3. Prepare Phase C by mixing the PVP K30 film former with the        deionized water of Phase C in the separate stainless steel        beaker at room temperature and then add the mixture to the batch        formed by the mixture of Phase A and Phase B.    -   4. Add the pigments (Phase D) slowly to the batch until a        substantial amount of dispersion has occurred, and then mill the        entire batch for 5 minutes at a gap setting of 20 using a        colloid mill.    -   5. Pour the output of the colloid mill into a stainless steel        beaker. Add the ingredients of phase E (triethanolamine,        lecithin, methylparaben) to the batch, heating to 75-80° C.,        using a water bath to heat the same and form a heated main        batch.    -   6. Mix phase F ingredients (wax-resin composite, and        emulsifiers) separately and heat to 80-85° C. using a water bath        with stirring using a propeller mixer to make a Phase F blend.        Slowly add the phase F blend to the main batch and mix for 15        minutes. Begin air cooling by removing the heat source. Cool to        40-45° C.    -   7. Mix the preservative phase (Phase G) until uniform by hand        stirring in a separate beaker to form a Phase G mixture. Add the        Phase G mixture to the batch, and continue mixing and begin        force cooling with ice and water bath to 30° C. Package into        appropriate vials.

Example 14 Cosmetic Lip Gloss Incorporating the Wax-Resin CompositeQuaternary Example of an Anhydrous Product

Ingredients: % Wt. Hydrogenated Polycyclopentadiene and Ceresin Wax (orother 10.00 products of examples 1-8) and Candelilla Wax and ParaffinWax and Tocopherols Permethyl 102A (solvent) 71.50 Ceraphyl 368 (ISP)(octyl palmitate) (emollient) 10.00 Ceraphyl 55 (ISP) (tridecylneopentanoate) (emollient) 5.00 Prisorine 2039 (Uniqema) (isostearylisostearate) (spreading 3.00 agent) LiquiPar Oil (ISP) (isopropylparaben(and) isobutylparaben 0.50 (and) butylparaben) (preservative) 100.00Procedure:

-   1. Mix all ingredients (wax-resin composite, oils, esters,    preservative, etc.) at room temperature in a 250 ml stainless steel    beaker using a Caframo mixer.-   2. Heat the batch slowly to 70-75° C. in a water bath with slow    stirring using a Caframo propeller stirrer until the mixture is    uniform.-   3. Once the batch appears homogenous, allowed to cool to 45° C., by    removing beaker from heated water bath, and add flavor and color if    desired.-   4. Package into appropriate containers.

Example 15 Cosmetic Eyeliner Pencil Incorporating the Wax-ResinComposite Ternary Example of an Anhydrous Product

Ingredients: % Wt. Permethyl 102A (solvent) 49.50 HydrogenatedPolycyclopentadiene and (or any product of 10.00 Polyethylene andCarnauba and Tocopherols examples 1-8) Ozokerite (gelling agent) 12.00Polyethylene (gelling agent) 4.00 Carnauba (structural agent) 3.50Stearyl Alcohol (emollient) 2.00 Beeswax (thickener) 5.00 TitaniumDioxide 35/65 pre-ground slurry (colorant) 2.00 Ultramarine Blue 35/65pre-ground slurry (colorant) 12.00 100.00Procedure:

-   1. Add all ingredients (wax-resin composite, solvent, additional    waxes, colors, etc.) to a 600 ml stainless steel beaker in a water    bath.-   2. Mix using a propeller stirrer at ambient temperatures until all    materials are dispersed evenly. Begin heating to 85° C. and continue    mixing.-   3. Once all the waxes have melted to produce a uniform dispersion,    remove the batch from the heat source. Immediately fill the batch    into stainless steel containers. After product has sufficiently    cooled, extrude into pencil form.

Example 16 Cosmetic Mascara Incorporating the Wax-resin CompositeTernary Example of a Water-in-oil Product

Phase 1. Hydrogenated Polycyclopentadiene 12.00 (or any product of (and)Carnauba Wax and Polyethylene examples 1-8) (and) TocopherolsIsododecane 42.73 (solvent) Phase 2. Lucentite SAN-P 2.00(thickener/stabilizer) Ethyl Alcohol 39C 1.00 (polar additive) Phase 3.Black Iron Oxide 5.00 (colorant) Cyclomethicone (and) PEG/PPG-20/15 5.00(emulsifier/ Dimethicone surfactant) Phase 4. Black 2WBG45 (Carbon Black(and) 5.00 (dispersed colorant) Butylene Glycol (and) Water) DeionizedWater 15.00 (solvent) Sodium Chloride 0.25 (stabilizer) Phase 5. C18-36Triglycerides 5.00 (thickener) White Beeswax 6.00 (thickener) Phase 6.Phenoxyethanol, Methylparaben, 1.00 (preservative) Propylparaben &Ethylparaben Vanillin USP 0.02 (fragrance) 100.00Procedure:

-   1. Combine Phase 1 materials (wax-resin composite and solvent) and    heat to 70° C. in a water bath.-   2. Add the Lucentite SAN-P (suspending/stabilizer) from Phase 2    slowly to Phase 1. Stir with a dispersator in a 600 ml stainless    steel beaker at high speed for 20 minutes. Add the ethanol from    Phase 2 and stir an additional 20 minutes. Gel formation should take    place which leads to a thickening of the main batch.-   3. Separately combine the emulsifier and black iron oxide of Phase 3    together to make a Phase 3 mixture and stir for 10 minutes using a    dispersator. Then add the Phase 3 mixture to the main batch.    Continue heating to 80-85 C.-   4. Separately combine the ingredients of Phase 4 with a propeller    mixer and then heat to 80-85 C while continuing to mix with a    propeller mixer. After the ingredients in the Phase 4 mixture are    well mixed, add the Phase 4 mixture thus produced) very slowly to    the main batch and stir at high speed with a dispersator for 45    minutes, maintaining the temperature at 80-85° C.-   5. Combine the triglycerides and wax of Phase 5 in a separate    beaker, heating with a water bath to 80° C. to form a Phase 5    mixture. Add the Phase 5 mixture to the main batch and continue to    disperse while heating to 85-87° C.-   6. Begin air cooling, for example by removing the hot water bath and    allowing the main batch to cool.-   7. At 65° C., take the weight of the main batch and add Isododecane    to make up for solvent loss. Force cool with an ice bath to 42° C.-   8. At 42° C. add Phase 6, the preservatives and vanillin.-   9. Continue mixing and cool to 25° C. Fill into appropriate    containers.

Example 17 Cosmetic Face Powder Incorporating the Wax-Resin CompositeTernary Example of a Cosmetic Powder

Ingredient Listing Part A. Mica (and) Isopropyl Titanium Triisostearate62.27 (base powder (GMS-I2) component) Yellow Iron Oxide(and) IsopropylTitanium 0.24 (colorant) Triisostearate (BYO-I2) Red Iron Oxide (and)Isopropyl Titanium 0.24 (colorant) Triisostearate (BRO-I2) Methylparaben0.15 (preservative) Part B. Hydrogenated Polycyclopentadiene (and) 4.00(or any product of Carnauba Wax and Polyethylene (and) Exs. 1-8)Tocopherols Pentaerythritol Tetraoctanoate 4.50 (emollient binder)Dimethicone(and)Trimethyl Siloxy Silicate 18.60 (binder) SilicaMSS-500/3H 10.00 (soft focus/optical agent) 100.00Procedure:

-   1. Combine the ingredients of Part A and mix thoroughly with a    spatula.-   2. Pass the premixed Part A pigment phase through a pulverizer or    blender until the color is fully extended.-   3. Mix the binder ingredients of Part B) in a beaker and put the    beaker in a heated water bath. Pre-blend the binder phase (Part B)    heating to 70-75° C. in a small stainless steel beaker with a    propeller-type mixer until the wax-resin composite is dissolved.-   4. Spray or add the binder (Part B) in very small increments to Part    A slowly, mix, and pass through a pulverizer or blender until oil    and wax-resin composite is dispersed.-   5. Press into cakes in appropriate pans and package.

What is claimed is:
 1. A process for making a pharmaceutical or cosmetic composition, comprising the steps of: (a) making a solid wax-resin composite wherein said making of said solid wax resin composite comprises combining: (i) hydrogenated polycyclopentadiene (ii) a wax, wherein said wax comprises at least one abhesive wax having a melting point range of 55° C. to about 115° C., (b) processing the solid wax-resin composite into powder, granules, prills, flakes or other particulates; and (c) blending said wax-resin composite into a pharmaceutical or cosmetic composition.
 2. The process according to claim 1 wherein the wax-resin composite is pumped through a pastillator, forming transparent solid pastilles.
 3. The process according claim 1, wherein the wax comprises a first wax, said first wax being a synthetic wax having a melting point of about 55° C. to about 115° C.; and a second wax as a blending agent, said second wax comprising a natural wax containing hydrocarbons to provide miscibility, and wherein said second wax has a lower melting point than the first wax.
 4. The process according to claim 3, wherein the first wax is polyethylene and the second wax is Carnauba wax.
 5. A process according to claim 1 wherein the hydrogenated polycyclopentadiene having a refractive index of 1.55-1.57.
 6. A process for making a cosmetic composition comprising the steps of: (a) at least partially solvating hydrogenated polycyclopentadiene in a solvent under the application of heat in the range of 80-85° C. resulting in a resin-solvent blend; (b) preparing a composition of wax, wherein said wax comprises at least one abhesive wax having a melting point range of 55° C. to about 115° C.; (c) mixing said resin-solvent blend and said wax to form a wax-resin blend; (d) removing the solvent from said wax-resin solution to produce a solid wax-resin composite; and (e) blending said wax-resin composite with materials selected from the group consisting of pigments, pharmaceuticals, oils, esters and sunscreens.
 7. A method for producing a solid wax-resin composite comprising: (a) melting hydrogenated polycyclopentadiene resin; (b) blending together the melted hydrogenated polycyclopentadiene resin with waxes at a temperature sufficient to melt the waxes, said wax comprising at least one of a first wax selected from the group consisting of crystalline polyethylene waxes, synthetic waxes, hydrocarbon waxes, petroleum waxes and mixtures thereof, and a second wax selected from the group consisting of natural or synthetic waxes containing hydrocarbons or hydrocarbon-like structures; (c) allowing the blended hydrogenated polycyclopentadiene resin and waxes to solidify into a wax-resin composite; and (d) post-processing the wax-resin composite to form slabs, pastilles, flakes or other solid forms.
 8. A method as in claim 7 wherein the hydrogenated polycyclopentadiene resin has a refractive index of 1.55-1.57.
 9. A method as in claim 8, wherein said temperature sufficient to melt the waxes is below 125° C.
 10. A method as in claim 9, wherein said post processing includes mechanically breaking up said solidified blended hydrogenated polycyclopentadiene resin and waxes.
 11. A method as in claim 10, wherein the hydrogenated polycyclopentadiene resin is melted with an antioxidant.
 12. A method as in claim 11, wherein the antioxidant comprises tocopherols. 